86633-42-3Relevant academic research and scientific papers
MEASUREMENT OF REACTION RATE CONSTANTS IN THE LIQUID CHROMATOGRAPHIC REACTOR: MASS TRANSFER EFFECTS.
Chu,Langer
, p. 1617 - 1625 (1986)
The adaptation of liquid chromatographic columms are chemical reactors for reaction kinetic studies is examined. The overall rate constants, k (apparent), for pyridine and 4-picoline catalyzed esterification reactions of tetrachloroterephthaloyl chloride
The Liquid Chromatographic Reactor for Kinetic Studies
Bolme, Mark W.,Langer, Stanley H.
, p. 3363 - 3366 (1983)
It is shown that a liquid chromatographic column can be used to generate a reactor chromatogram.The data of the chromatogram can then be utilized to calculate kinetic rate constants if the composition of the stationary phase is considered.Further study sh
CHARACTERIZATION OF A CHEMICALLY BONDED STATIONARY PHASE WITH KINETICS IN A LIQUID CHROMATOGRAPHIC REACTOR.
Chu,Langer
, p. 2197 - 2204 (1985)
Liquid chromatographic columns are shown to be operable as chemical reactors for investigating solute-stationary phase interactions in reversed-phase systems. The kinetics of several organic base-catalyzed esterification reactions of tetrachloroterephthal
Study of the Kinetics and Mechanism of the Base-Catalyzed Esterification of Tetrachloroterephthaloyl Chloride with HPLC and Carbon-13 FT-NMR
Langer, Stanley H.,Chu, Alexander H. T.,Bolme, Mark W.,Turner, Michael S.,Quinting, Gregory R.
, p. 3601 - 3648 (2007/10/02)
The pyridine base-catalyzed esterification of tetrachloroterephthaloyl dichloride (R) with methanol was studied at room temperature and found to follow a four-step course; high-perfomance liquid chromatography (HPLC) was used to analyze and characterize intermediates in reaction mixtures.The reaction proceeds with the initial formation of a benzoylpyridinium ion (M) followed by formation of a terephthaloyl dipyridinium ion (N); both are strongly associated with the alcohol solvent molecules as indicated by chromatographic retention times.The pyridinium salts react with alcohol to form a monoester followed by product diester (P) at slower rates.The rate constants for each mechanistic step were obtained from batch reactor studies together with HPLC analysis; the rates for the first two consecutive steps were dependent on the organic base (pyridine and 4-picoline) catalyst concentration.Large, negative values of the entropy of activation were interpreted in terms of a highly ordered transition state in the course of formation of the ionic intermediates.The presence of alcohol was found to be important for the formation of the salts.Carbon-13 FT-NMR spectra of polychlorinated reaction intermediates were obtained at low temperature to enhance sensitivity; results supported conclusions regarding structures and reaction requirements.
